CN104817891B - Write-through nano-silver conductive ink and preparation method thereof - Google Patents
Write-through nano-silver conductive ink and preparation method thereof Download PDFInfo
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- CN104817891B CN104817891B CN201510170700.XA CN201510170700A CN104817891B CN 104817891 B CN104817891 B CN 104817891B CN 201510170700 A CN201510170700 A CN 201510170700A CN 104817891 B CN104817891 B CN 104817891B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/16—Writing inks
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/52—Electrically conductive inks
Abstract
The invention discloses white-through nano-silver conductive ink which comprises, by weight, 5-60% of silver nanoparticles coated with an anionic surfactant and 40-95% of an ink solvent. The ink solvent is composed of a solid A and a solid B according to the mass ratio of 1: (0.01-0.001), wherein the solid A is selected from at least one of 1,2-propylene glycol, triethanolamine, oleic acid and deionized water; and the solid B is selected from at least one of benzotriazol, 2,2-dibromo-2-cyanoacetamide and hydroxyethyl cellulose. A preparation method of the white-through nano-silver conductive ink is simple and easy to operate. Viscosity of the white-through nano-silver conductive ink at 20 DEG C is 100-500 mPa.s, and surface tension of the white-through nano-silver conductive ink at 20 DEG C is 30-50 mN.m＜-1＞. A circuit prepared by the use of the white-through nano-silver conductive ink has excellent conductivity and adhesiveness. The conductive ink can be applied to a flexible substrate. Thus, range of application of the conductive ink to printed electronics is broadened.
Description
Technical field
The invention belongs to printed electronics field, and in particular to a kind of write-through nano silver conductive ink and its preparation side
Method.
Background technology
As printing technology develops to the direction such as flexibility, portable, wearable and inexpensive, with plastics, paper, cloth
The flexible materials such as material are also being continuously increased as the circuit requirements of substrate.In addition to conventional printed circuit methods, ball is copied
Pen is prepared carrying out simple direct write circuit, even more one convenient flexible circuit connection means.
In early days, Janpanese Printing Co., Ltd adopts felt tip pen (JP07276878A), pours into silver-colored ink to prepare circuit,
But the felt tip pen of similar brush pen, ink amount are not easily controlled, and fineness is also poor, and electricity prepared by its electrically conductive ink for adopting
Road square resistance is up to 30M Ω/.(Xu, the L.Y. such as Xu；Yang,G.Y.；Jing,H.Y.；Wei,J.；Han,
Y.D.Pressure-assisted low-temperature sintering for paper-based writing
2013,24,355204.) silver nano-grain of preparation is dispersed in ethanol, second two by electronics.Nanotechnology
In the mixed liquor of alcohol and glycerol, silver inks water is prepared, be then injected in sign pen core, draw pattern in photo papers, passed through
120 DEG C, 25MPa hot pressed sinterings are after 15 minutes, the resistivity of the conducting wire of preparation is 14.3 μ Ω cm, about block silver electricity
9 times of resistance rate, but the use of hot-press sintering equipment, seriously limit the range of application of the conductive stylus.Magdassi etc.
(Magdassi,S.；Grouchko,M.；Berezin,O.；Kamyshny,A.Triggering the Sintering of
Silver Nanoparticles at Room Temperature.ACS Nano 2010,4,1943-1948.) propose chemistry
The method of sintering Argent grain, prints silver in the plastic-substrates for soaking diallyl dimethyl ammoniumchloride (PDAC) solution
Grain ink is preparing silver-colored conducting wire, but need to first soak in the solution substrate, and process is cumbersome, while the bases such as paper can be destroyed
Bottom.
On the one hand, the method for improving metallic conduction stability of ink is by adding protective agent realizing.In metal nano
The macromolecule dispersant added in particle preparation or metallic conduction ink preparation process is interacted simultaneously with metal nanoparticle
Metal nanoparticle surface is coated on, so as to prevent the contact between granule and granule, the stability of metallic conduction ink is improved.
But on the other hand, the protective agent of metal nanoparticle surface cladding, often affects electronics metal nanoparticle in the coating
Between transmission, printing write after circuit, it is necessary to have a last handling process (such as heat) to promote particles sintering, improve
The electric conductivity of circuit.As macromolecule dispersant polyvinylpyrrolidone, be conducive to improving the stability of ink, but its post processing temperature
Up to 200 DEG C of degree, limits its application in the flexible substrates such as plastics and paper；As lower alkyl amine protective agent, although
Post-processing temperature at 140 DEG C, but as the active force between the protective agent and metal nanoparticle is weaker, can cause the ink again
Bad stability.
The content of the invention
The technical problem to be solved is, for the deficiencies in the prior art, there is provided a kind of write-through nanometer silver is led
Electric ink and its simple preparation method, the nano silver conductive ink can be using inkjet printing, the medium direct writing means of the injection shaft of a writing brush
Circuit is prepared in flexible substrates such as plastics, paper, the circuit can obtain without the need for post processings such as sintering that electric property is good leads
Circuit.
The present invention solve the technical scheme that adopted of above-mentioned technical problem for：A kind of write-through nano silver conductive ink, its
Mass percent composition includes：Surface coating has a silver nano-grain 5～60% of anion surfactant, and ink solvent 40～
95%, described ink solvent presses 1 by A class I liquid Is and B classes solid：(0.01-0.001) mass ratio composition, described A class liquid
At least one of the body in 1,2- Propylene Glycol, triethanolamine, Oleic acid and deionized water；Described B classes solid is three nitrogen of benzo
Azoles, 2,2- dibromo-2-cyanoacetamides and hydroxyethyl cellulose.
At least one of the A class I liquid Is in 1,2-PD, triethanolamine, Oleic acid and deionized water, wherein, 1,2- third
Glycol, triethanolamine and Oleic acid are oil-based liquid, are conducive to that the flowing of ink is smooth stable, and deionized water meets environmental protection
Requirement.B classes solid is BTA, DBNPA and hydroxyethyl cellulose, wherein, three nitrogen of benzo
Azoles and DBNPA are electrophilic monomer, in the ink curing processes write out, electrophilic monomer with
The anion surfactant neutralization on silver nano-grain surface, and then induce the reunion of silver nano-grain, sintering, hydroxy ethyl fiber
Element can change the viscosity of ink, to meet the use needs in different application field.
The particle diameter of described silver nano-grain is less than 60nm.
In above-mentioned write-through nano silver conductive ink, described anion surfactant is selected from polyglutamic acid, polypropylene
One or two in acid, polymethylacrylic acid, polyoxypropylene, fatty alcohol-polyoxyethylene ether and polyoxyethylated alkyl phenol.It is poly-
Glutamic acid, polyacrylic acid anion surfactant can make that silver nano-grain surface is negatively charged, and between silver nano-grain, electrostatic is scolded
The interaction of power makes conductive ink performance more stable.
A kind of preparation method of above-mentioned write-through nano silver conductive ink, comprises the following steps：
(1) A class I liquid Is and B classes solid are pressed into 1：(0.01-0.001) mass ratio mixing, stirring obtain ink solvent；
(2) adding Surface coating in ink solvent has the silver nano-grain of anion surfactant, obtains mixing molten
Liquid；
(3) mixed solution is stirred into 1-4 hours, obtains the write-through nano silver conductive ink of stable performance.
In the preparation method of above-mentioned write-through nano silver conductive ink, described anion surfactant is selected from polyglutamic
One kind in acid, polyacrylic acid, polymethylacrylic acid, polyoxypropylene, fatty alcohol-polyoxyethylene ether and polyoxyethylated alkyl phenol
Or two kinds.
Compared with prior art, it is an advantage of the current invention that：The invention discloses a kind of write-through nano silver conductive ink,
Its preparation method is simple, easy to operate；Viscosity of the write-through nano silver conductive ink of the present invention at 20 DEG C is 100-500mPa
S, surface tension are 30-50mN m-1.Suitable ink viscosity and surface tension are conducive to inkjet printing or the injection of ink
Direct write in the shaft of a writing brush and be unlikely to generation and be difficult to spray or the counter productive such as leak；Write-through nano silver conductive ink of the present invention can
Circuit is prepared using inkjet printing, the medium direct writing means of the injection shaft of a writing brush in flexible substrates such as plastics, paper, the circuit is without the need for sintering
The good conducting channel of electric property can be obtained Deng post processing；The electricity prepared using write-through nano silver conductive ink of the present invention
Road has excellent electric conductivity and adhesiveness, can be applicable to flexible substrates, expands application of the conductive ink on printed electronic
Scope.
Description of the drawings
Fig. 1 is the optics shape for writing circuit using the write-through nano silver conductive ink of embodiment 1 on A4 printing papers
Looks figure；
Fig. 2 is in polyethylene terephthalate (PET) plastics using the write-through nano silver conductive ink of embodiment 1
The optical morphology figure for writing circuit in substrate；
Fig. 3 a, 3b, 3c are that the circuit of writing using the write-through nano silver conductive ink of embodiment 1 on ivory board is distinguished
The dried scanning electron microscope diagram under the conditions of room temperature, 100 DEG C/10 minutes, 150 DEG C/10 minutes；
Fig. 4 is between the rate of drying and resistance of the circuit that the write-through nano silver conductive ink of embodiment 1 is write out
Graph of relation；
Fig. 5 is the resistance variations situation for adhering to conducting wire during 10000 times using 3M adhesive tapes.
Specific embodiment
The present invention is described in further detail below in conjunction with accompanying drawing embodiment.
The preparation method of the write-through nano silver conductive ink of embodiment 1 is：
(1) by 0.06g BTAs, 0.04g DBNPAs and 0.5g hydroxyethyl celluloses add
Enter to 5.2g 1,2-PDs, 0.22g triethanolamine, in 0.16g Oleic acid and 53.82g deionized waters, stirring and dissolving obtains ink
Aqueous solvent, quality are 60g；
(2) in ink solvent, adding Surface coating has the silver nano-grain 40g of anion surfactant, is mixed
Close solution；
(3) mixed solution is stirred 3 hours, obtains the write-through nano silver conductive ink of stable performance.
In being 380 μm of clean pen core by write-through nano silver conductive ink obtained above injection written diameter of the steel ball,
Obtain conductive ink water-color paintbrush.
Conducting wire is drawn on common A4 printing papers using the conductive ink water-color paintbrush, and the optics picture of drawn conducting wire is as schemed
Shown in 1.The section thickness of the film layer that sweep electron microscopic measure conductive ink is formed is combined using four probe method, the conduction is calculated
The resistivity of circuit is 14.2 μ Ω cm.
Conducting wire is drawn using the conductive ink water-color paintbrush in polyethylene terephthalate (PET) plastic-substrates, it is drawn
The optics picture of conducting wire is as shown in Figure 2.The film layer that sweep electron microscopic measure conductive ink is formed is combined using four probe method
Section thickness, the resistivity for calculating the conducting wire are 16.7 μ Ω cm.
Four probe method measures the principle of metal pattern：The needle point of four probes touches metal pattern surface, four probes simultaneously
Two, outside probe constant-current source be connected, the probe of inner side two of four probes is connected on voltmeter.When electric current is from constant-current source
When flowing through two probes in outside of four probes, the voltage for flowing through metal pattern generation can be read from voltmeter.Metal pattern
Resistivity computing formula is：
Wherein, resistivity of the ρ for metal pattern；I is the electric current for flowing through metal pattern, is provided by constant-current source；V is electric current stream
The voltage produced during Jing metal pattern prints, is read by voltmeter；D is the thickness of metal pattern, can be drawn by scanning electron microscope.
In order to further illustrate the room temperature writing effect of write-through nano silver conductive ink, using the conductive ink water-color paintbrush in card
Conducting wire is drawn on piece paper, then by drawn conducting wire respectively under the conditions of room temperature, 100 DEG C/10 minutes, 150 DEG C/10 minutes
It is dried or sinters, the scanning electron microscopic picture of dried conducting wire is respectively as shown in Fig. 3 a, Fig. 3 b and Fig. 3 c.From Fig. 3 a, figure
As can be seen that as the rising of sintering temperature, the morphology change of silver nano-grain are less, illustrating using the present invention in 3b, Fig. 3 c
Conducting wire prepared by nano silver conductive ink has excellent adhesiveness and stability；Measure in addition its corresponding resistivity according to
Secondary is 15.2 μ Ω cm, 14.8 μ Ω cm, 14.2 μ Ω cm, is changed less, it is seen that sintering temperature is received to write-through of the present invention
The impact very little of the silver-colored conductive ink conductivity of rice, illustrates even without sintering step, using nano silver conductive ink of the present invention
The conducting wire of preparation still has preferable conductivity, and Fig. 4 is the electricity that the write-through nano silver conductive ink of embodiment 1 is write out
Graph of relation between road rate of drying and resistance, illustrates the circuit rate of drying that write-through nano silver conductive ink is write out
Hurry up, be 260000 Ω when its resistance is dried 1 minute, and resistance drops to 193 Ω after being dried 30 minutes.
Tested using the adhesiveness of silver-colored conducting wire of the 3M adhesive tapes to direct write in substrate, the silver-colored conducting wire of measurement
Resistance (R-R0)/R0With the change of adhesion number of times, wherein R is conducting wire resistance after adhesion, R0It is initially electric for conducting wire
Resistance.Fig. 5 is the resistance variations situation for adhering to conducting wire during 10000 times using 3M adhesive tapes, even if from fig. 5, it can be seen that
Adhered to 10000 times using 3M adhesive tapes, the resistance variations of conducting wire prepared by nano silver conductive ink of the present invention are only 2.5%,
Illustrate that conducting wire is strong with the adhesion of substrate, does not fall off substantially.
Therefore, write-through nano silver conductive ink of the present invention has preferable writing effect at room temperature, using the present invention
Circuit prepared by write-through nano silver conductive ink has excellent electric conductivity, adhesiveness and stability, can be applicable to various soft
Property substrate.
The preparation method of the write-through nano silver conductive ink of embodiment 2 is：
(1) by 0.05g BTAs, 0.02g DBNPAs and 0.02g hydroxyethyl celluloses add
Enter to 26g 1,2-PDs, 1.1g triethanolamine, in 0.8g Oleic acid and 67.01g deionized waters, it is molten that stirring and dissolving obtains ink
Agent, quality are 95g；
(2) in ink solvent, adding Surface coating has the silver nano-grain 5g of anion surfactant, is mixed
Solution；
(3) mixed solution is stirred 4 hours, obtains the write-through nano silver conductive ink of stable performance.
The preparation method of the write-through nano silver conductive ink of embodiment 3 is：
(1) by 0.03g BTAs, 0.01g DBNPAs and 0.01g hydroxyethyl celluloses add
Enter to 30g 1,2-PDs, 2g triethanolamine, in 1g Oleic acid and 36.01g deionized waters, stirring and dissolving obtains ink solvent,
Quality is 70g；
(2) in ink solvent, adding Surface coating has the silver nano-grain 30g of anion surfactant, is mixed
Close solution；
(3) mixed solution is stirred 1 hour, obtains the write-through nano silver conductive ink of stable performance.
In above-described embodiment, used Surface coating has the preparation of the silver nano-grain of anion surfactant, can be with
Method described in the patent of invention of Publication No. CN102816462A declared with reference to the applicant.
Claims (3)
1. a kind of write-through nano silver conductive ink, it is characterised in that its mass percent composition includes：Surface coating have it is cloudy from
The silver nano-grain 5～60% of sub- surfactant, ink solvent 40～95%, described ink solvent is by A class I liquid Is and B classes
Solid presses 1：(0.01-0.001) mass ratio composition, described A class I liquid Is selected from 1,2-PD, triethanolamine, Oleic acid and
At least one in deionized water；Described B classes solid is BTA, 2,2- dibromo-2-cyanoacetamides and ethoxy
Cellulose；Described anion surfactant is selected from polyglutamic acid, polyacrylic acid, polymethylacrylic acid, polyoxypropylene, fat
One or two in polyoxyethylenated alcohol and polyoxyethylated alkyl phenol.
2. a kind of write-through nano silver conductive ink according to claim 1, it is characterised in that described silver nano-grain
Particle diameter be less than 60nm.
3. the preparation method of the write-through nano silver conductive ink described in a kind of claim 1 or 2, it is characterised in that including following
Step：
(1) A class I liquid Is and B classes solid are pressed into 1：(0.01-0.001) mass ratio mixing, stirring obtain ink solvent；
(2) adding Surface coating in ink solvent has the silver nano-grain of anion surfactant, obtains mixed solution；
(3) mixed solution is stirred into 1-4 hours, obtains the write-through nano silver conductive ink of stable performance.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510170700.XA CN104817891B (en) | 2015-04-13 | 2015-04-13 | Write-through nano-silver conductive ink and preparation method thereof |
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| CN201510170700.XA CN104817891B (en) | 2015-04-13 | 2015-04-13 | Write-through nano-silver conductive ink and preparation method thereof |
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| CN104817891B true CN104817891B (en) | 2017-03-22 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106634220A (en) * | 2016-09-13 | 2017-05-10 | 江南大学 | Environmental friendly nano silver conductive ink and preparation method and printing application thereof |
| CN106752365A (en) * | 2016-12-02 | 2017-05-31 | 曲阜师范大学 | A kind of water-proof environmental protection prepared Chinese ink and preparation method thereof |
| EP3385342B1 (en) * | 2017-04-03 | 2020-03-25 | Nano and Advanced Materials Institute Limited | Water-based conductive ink for rapid prototype in writable electronics |
| CN108847359B (en) * | 2018-06-27 | 2020-11-13 | 暨南大学 | Preparation method and application of direct-writing CNT/Ag flexible supercapacitor |
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| JP3320940B2 (en) * | 1994-03-31 | 2002-09-03 | 三菱製紙株式会社 | Lithographic printing plate processing method |
| CN102504647A (en) * | 2011-10-31 | 2012-06-20 | 天津大学 | Conductive ink based on nano metal and application thereof in different jet printing methods and photographic paper |
| CN102816462B (en) * | 2012-08-13 | 2014-04-16 | 中国科学院宁波材料技术与工程研究所 | Preparation method for nano-silver particles coated with organic protection agent on surfaces |
| CN103194117B (en) * | 2013-04-08 | 2014-12-03 | 电子科技大学 | Preparation method and application of sintering-free ultrafine silver nanometer printing ink |
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